Patent GB-1269660-A (GB)
Title: Improvements in or relating to glycol derivatives and the manufacture thereof
IPC: C07C405/00
Filed: 1969-07-22
Abstract: 1,269,660. Bicyclo [3,1,0] hexane derivatives. UPJOHN CO. 22 July, 1969 [29 July, 1968 (3)], No. 7127/71. Divided out of 1,269,656. Heading C2C. The invention comprises novel bicyclo [3,1,0]- hexane derivatives of the formula in oxo or endo configuration with respect to the C(OH)R 4 -C(OH)R 2 R 3  moiety, wherein R 2  is H or C 1-8  alkyl,substituted with 0 to 3 fluorine atoms, R 3  and R 4  are H or C 1-4  alkyl, C n H 2n  is C 1-8  alkylene substituted with 0 to 2 fluorine atoms, # indicates attachment of the C n H 2n COOR 1  moiety to the ring in alpha or beta configuration, R 1  is H, C 1-8  alkyl, C 3-10  cycloalkyl, C 7-12  aralkyl, phenyl, or phenyl substituted by 1 to 3 chlorine atoms or C 1-4  alkyl, or ethyl substituted in the beta position with 3 chlorine atoms, 2 or 3 bromine atoms, or 1, 2 or 3 iodine atoms, the corresponding bis-alkane sulphonic acid esters, wherein the sulphonic acid ester grouping is SO 2 R 6 , wherein R 6  is C 1-5  alkyl and the corresponding mono alkane sulphonic acid esters, wherein the free OH is on the carbon adjacent the cyclopropane ring with the proviso that R 1  is only H when both OH groups are unesterified. The compounds are prepared as shown in the following scheme. wherein R 7  is as R 1  except it cannot represent a hydrogen atom. The transformation of olefin XXIV to glycol XXVI is carried out by reacting said olefin with a hydroxylating reagent. Transformation of Formula XXV epoxide to glycol XXVI is carried out by reacting said epoxide with an acid with pK less than 4. Glycol XXVI is converted to the corresponding bis-alkanesulphonic acid ester of Formula XXVII by reaction of XXVI with an alkylsulphonic chloride or bromide, or with an alkanesulphonic acid anhydride. Monosulphonic acid esters are formed as by-products when the bis-sulphonic esters are reacted with water at 0‹ to 60‹ C. or heated in the range of 40‹ to 100‹ C. with a combination of water, a base characterized by its water solution having pH 8 to 12, and sufficient inert water-soluble organic diluent to form a basic and substantially homogeneous reaction mixture. The following intermediates and starting materials are also prepared:- 6 - Exo - (11 - cis - heptenyl - 2α - (6<SP>11</SP> - carboxyhexyl) - bicyclo - [3,1,0] - hexane - 3 - one, 6 - oxo - (1<SP>1</SP> - cis - heptenyl) - 2# - (6<SP>11</SP> - carboxyhexyl) - bicyclo - [3,1,0] - hexane - 3 - one, and the corresponding endo isomers; 6-carbethoxybicyolo - [3,1,0] - hexan - 3 (and 2)-ol, and the tetrahydro pyranyl esters thereof; endobicyclo - [3,1,0] - hexane - 3 (and 2)-ol-6-carboxylic acid methyl ester and corresponding tetrahydropyranyl ethers; endo-6-hydroxymethyl bicycle - [3,1,0] - hexan - 3 (and 2).ol-3- (and 2)-tetrahydropyranyl ethers; endo-bicyclo- [3,1,0] - hexan - 3 (and 2) - ol - 6 - carbonaldehyde-3 (and 2)-tetrahydropyranyl ethers; endo - 6 - (cis- and trans - 1 - heptenyl)-bicyclo- [3,1,0] - hexan - 3 (and 2) - ol tetrahydropyranyl ethers; endo - 6 - (cis- and trans-1- heptenyl) - bicyclo - [3,1,0] - hexan - 3 (and 2) - ol; endo - 6 - (cis- and trans - 1 - heptenyl)- bicyclo - [3,1,0] - hexan - 3 - one; end - 6 - (cis- and trans - 1 - octenyl) - bicyclo - [3,1,0]-hexan-3 (and 2)-ol and the tetrahydropyranyl ethers thereof; endo - 6 - (cis- and trans - 1 - octenyl)- bicyclo - [3,1,0] - hexan - 3 - one; methyl 6- endo - (1 - octenyl) - 3 - oxobicyclo - [3,1,0]- hexane - 2 - heptanoate; methyl 6-endo-(7- methyl - 1 - octenyl) - 3 - oxobicyelo - [3,1,0]- hexane - 2 - heptanoate; methyl 6-endo-(6,6- dimethyl - 1 - heptenyl) - 3 - oxobicyclo-[3,1,0]- hexane - 2 - heptanoate; methyl 6-endo-(1- hepentyl) - 3 - oxobicyclo - [3,1,0] - hexane-2- (2,2 - dimethylheptanoate; methyl 6-endo - (1- heptenyl) - 3 - oxobicyelo - [3,1,0] - hexane-2- (3,3 - dimethylneptanoate; methyl 7 - iodo-3,3- dimethylheptanoate; methyl 7-chloro-3,3-dimethylheptanoate; 7-chloro-3,3-dimethylheptanoic acid and methyl 7-[endo-6-(1.heptenyl)- 3-oxobicyclo-[3,1,0]-hex-2-yl]-heptanoate.